Naphthenic acid-modified alkyd resin



l atent ed July 23, 1946 Per K. Frolich, Westfleld, N. 1., assignor toStandard Oil Development Company, a corporation of Delaware N Drawing.

Application October 27, 1936,

Serial No. 107,800

4 Claims.

This invention deals with the preparation of resinous compoundscontaining naphthenate groups. More specifically, it deals'with themodification of various organic resins with naphthenic compounds, suchas those produced from petro-' leum oils, to give distinctive andsuperior properties to such resins.

At the present time the greatest source of naphthenic acids is frompetroleum. These natl0 urally occurring materials, which are preferredover other naphthenic acids such as those of the synthetic type, aregenerally recovered in a crude state by fractionally distilling thecrude oil and neutralizing the fractions which take overhead most of theacids, such fractions being generally the kerosene, gas oil and lightlubricating oil cuts. The soaps so produced are then treated withsulfuric acid and the naphthenic acids are recovered by distillation. Anumber of crude q oils, such as those from California, Colombia and vRumania may contain upward of 2% or even more such acids in selectedfractions.

1 A sample of naphehtenic acids recovered in this manner from Colombiacrude gas oil fraction has 88 the following properties Gravity (A. P.I.) "13.4.

Flash -2'l0 F.

Neutralization value 186 mg. KOH/G. w Saponi'fication value 188 mg.KOH/G.

Water about' 1%.

Unsaponifiable matter .6.5% (mostly oil).

Ash 1 A sample of such acids having an acid numher of about 225 wasfractionated at 5 mm. pressure and saponification values on thefractions were obtained.

' 8a niilca- 0 Mn t on No.

85 0 183 185-196" 0 247 196-210" 0 249 210-220'0 220-238 O 241 45inc-248 o :1: 243 0. up.

.tion according to the method which will be substantially set forth.

The naphthenic acids are of value in preparing modified alkyd resinshaving distinctive properties. 1 For instance, one molecule of glycerol5 may be esterified with one molecule of naphthenic acids, and. theremaining "two hydroxy groups in the glycerol may be reacted withmaleic,

' adipic, succinlc, phthalic, or other dibasic acid.

In the case of phthalic acid or anhydrid'e, a 10 semi-solid thick resinis obtained which is highly suitable as a plasticizer for celluloseesters or ethers, alkyd resins, and the like. Harder resins may beprepared from maleic anhydride, using less ,4 to mol.) of naphthenicacids. In 16 many cases it, is advantageous to react the remainder ofthe molecule of the polyhydric compound with a drying acid such aslinoleic, linolenic, licanic, ricinoleic, or other fatty drying acids,fossil resins, or even a non-drying fatty an acid or with .both a dryingacid and'a polybasic acid.

Another valuable use for naphthenic acids in this field is as a modifierfor the usual water soluble dibasic acids which have been heretofore asconsidered unsuitable for the preparation of alkyd resins. For example,malic, tartaric or citric acid may be esterifled with naphthenic acidsor their anhydrides,- either partially or completely, and the productsso-iormed may then so be reacted with a polyhydroxy compound such asglycerol or glycol. In the case of glycerol, polyglycerols orpolyglycols, one or more of the hydroxy. grpups may be esterified withnaphthenic acids prior to resinification. as

It is to be understood that the term naphthenic acid is to be construedas covering both the acids and the anhydrides, although the latter arepreferable. Such anhydrides are most conveniently prepared by bubblingketene 40 through the acids, heating the complex formed,

and distilling of! acetic anhydride, leaving naphthenic anhydrides asbottoms.

Naphthenic vinyl resins having distinctive properties may also beprepared by esterifying ,5 polyvinyl alcohol with naphthenic acidanhydride. Such'resins possess much higher oil solubility than the usualvinyl resins.

Another class of resins which'may be improved by naphthenic'compoundsare those of the Diels- 50 Alder type of resin by reaction of diolefinsor cracked gasolines with maleic acid. Such products may be esteriiiedwith glycerol mononaphthenate to give highly desirable resinousproducts. e5

The naphthenic alcohols find value in the preparation of modifiedacrylic. or methacrylic ester polymers. The usual method for producingthe modified acrylic ester polymers is to react ethylene chlorhydrinwith sodium cyanide thereby obtaining thecyanhydrin which is dehydratedand hydrolyzed to the acid that may be esterified with naphthenicalcohol to give a naphthenic acrylate which may' then be polymerized byheating with a catalyst such as benzoyl peroxide.

Highly oil-soluble solid resins are thus produced.

to produce solid moldable resins which have superior water resistantproperties.

The above examples are merely illustrative of the many forms ofnaphthenic resins which may be prepared. Such products may be admixedwith other resins or fillers, pigments, inhibitors,

- dyes, plasticizers, plastics, rubbers, and the like.

The intention here is not to limit the invention to the examples givennor to the reaction mechanism, but only to the following claims whichare drawn up as broadly as the prior art permits.

I claim: 1. Composition of matter comprising an alkyd resin producedbyreacting not more than one mol. of naphthenic acid from petroleum withone mol. of a polyhydric aliphatic compound having more than twohydroxyl groups, and one mol. of

a dicarboxylic organic acid.

' 2. Method of producing a modified alkyd resin comprising reacting apolyhydroxy aliphatic alcohol containing more than two hydroxyl groupswith not more than one mol. of a petroleum naphthenic acid untilesterification is substantially complete, then reacting theresultingcompound with a polycarboxylic organic acid until substantiallycomplete esteriflcation is obtained.

3. Method of producing amodifled alkyd resin comprising reacting apolyhydroxy aliphatic a lcohol containing more than two hydroxyl groupswith less than one mol. of a petroleum naphthenic aciduntilesteriflcationis substantially complete, reacting the resultingcompound with an organic drying acid to esterify the hydroxy compoundincompletely so as to leave at least two unreacted hydroxyl groups permolecule, and completing the esterification of the hydroxy compound toresiniflcation with a polycarboxylic" organic acid. 1

4. Method of producing a modified alkyd resin comprising reacting onemol of glycerol with one sistency.

PER K. FROLICH.

